Catalyst and method of making the same.



MAN, a citizen of the madam.

v ALEXANDER SGHWABCMAN, 0F BUFFAIO, NEW YORK, ASSIGNOR T0 KEIIIIOGG' PM@6135, INC., OE'BUFFALO, NEW YORK, A CORPORATION OF NEW YORK. I

no Drawing To all whom it may concern:

Be it known that I ALEXANDER SCHWARC- United States, residing atBufi'alo, in the county of Erie and State of New York, have inventedcertain new and useful Improvements in Catalysts and Methods of Makingthe Same, of which the following is a specification.

This invention relates to catalysts and methods of making the same; andit comrises a method of making a catalyst suitable or simultaneouspurification, decolorizing and hardening of oils, either animal orvegetable, wherein fullers earth or other decolorizing powder isimpregnated with a solution of a nickel salt, is treated with analkaline precipitant containing a nitrogenous colloid such as wool, andis then reduced to give active nickel; and it also comprises as a newcomposition of matter a non-sliming decolorizing hydrogen-addingcatalyst composed of fullers earth and finely' divided nickel firmly andfixedly held therein; all as more fully hereinafter set forth and asclaimed,

In the hardening of oils, it is a common practice to treat the oil withhydrogen in the presence of freshly reduced nickel; this nickel beingused in different physical forms, as powder, as colloidal solution, asthin leaves, etc. Very frequently, the nickel is used with a carrier ordiluent, such as kieselguhr, charcoal, etc. The hardening is conductedat a rather high temperature and is apt to result in some darkening ofthe oil-it has no beneficial action on the color. After the hardening iscomplete, or has been carried to the extent desired, the nickel must ofcourse be removed; and in practice this removal is somewhat hard toeffect. This is due partly to the existence of some or all of the nickelin a colloidal form, rendering filtration with removal of nickeldificult. To some extent, it is due to the presence of nickel soaps insolution or quasi-solution and these are also dificult of removal.

Fullers earth is of course a good decoloricing agent for oils of allkinds, both mineral oils and animal and ve etable oils. In prac-'tice,.it is often used be ore or after the hardening for the purpose ofdecolorizing the oil. It has been proposed as a carrier for the nickelin the hardening itself but fullers earth is rather fine in its textureand the Specification of Letters Patent.

Application filed August 13, 1917. serial no. 1%,917.

CATALYST AND METHOD OF MAKING THE SAME.

nickel is apt to slime 0d. For this reason Patented (Pet. 11. rate.

other carriers, such as kieselguhr and charat coal, have been employed.With these carriers also the jdificulty, noted ante, of slim mg ofi"alsoijoccurs; being responsible, in part, for the dificulty infreeingthe oil of nlckel after the operation.

I have found that I can deposit the nickel 1n fullers earth in aparticular way and obtam a carrier-held catalyst in which the nickel isfixedly held even though it be in the state of fine subdivision which isnecessary for the greatest eficiency in hydrogenation. -In so doing, Iproduce a compound catalyst which has not only the hardening propertybut also the decolorizing property of fullers earth; and l am enabled tode-\ colorize and harden in one operation instead of dolng it, as isusual, in two. For

this purpose, I first impregnate the fullersearth with a soluble nickelsalt, which is, advantageously, the nitrate. Other salts may be used butthe nitrate I regard as the best.

I may use it in the form of a concentrated solution of the amount ofnickel required; the solution being in the amount that fullers earthwill take up readily. Weaker solutions in greater volumes maybe em-Eloyed and in' such event the mixture may e dried after the impregnationto secure the presence of a concentrated solution in the pores. Or'thefullers earth may be simply suspended in a solution of nickel nitrate,absorption being relied on to transfer the dissolved salt of nickel tothe pores and surfaces of the earth. The impregnated fullers earth isnext treated with a solution of caustic soda which forms nitrate of sodawhich remains in solution and a precipitated hydrate of nickel in thepores. If the caustic soda is used alone, however, ll find that theproduct does not have the described properties. On drying and reductiona catalyst is obtained having the nickel not permanently retained. Butby dissolving in the caustic soda solution a small amount of almost anyorganic nitrogenous colloid, the physical character of the precipitatein the pores and its relation to the fullers earth are so changed thatthe nickel is fixedly held. This efiect persists after drying andreducing the catalyst. A solution of 2 parts of ordinary wool in acaustic soda tlh solution containing 25 to 30 parts of soda in 200 partsof water, makes a good precipltant. After precipitation, the compoundcatalyst is washed to remove the soda, dried and is then reduced at alow temperature. I find that the decolorizing effect of fullers earth sotreated, that is, the power of removing the color giving constituents ofoil, is not forfeited; indeed it is somewhat enhanced by the treatment.

' In a specific embodiment of the present invention, I may suspend 100parts of commercial full ers earth in 1,000 parts of water by agitationand add 100 parts of commercial nickel nitrate dissolved in 300 parts ofwater. The temperature of the mixture is brought to about 180 Rand to itis added a precipitant made by dissolving 27 .5 parts of caustic soda in200 parts of water and adding 2 parts of wool. The reaction formscolloidal nickel hydrate which is taken upand firmly held by the fullersearth. The fullers earth may now be washed by decantation, filteredofi,pressed and dried. It is next reduced. This reduction need not be'at a particularly low temperature; temperatures of 500 to- 600 C. givinggood results.

Instead of wool, leather, glue, hair, gelatin, casein and egg albumenmay be employed in about the same quantity.

Inan alternative method, the fullers earth is impregnated with about theamount of nickel nitrate solution which it will take up,

treated with a caustic soda solution containing a dissolved organicnitrogenous colloid body, washed and dried. Washing should be until thealkaline reaction disappears. Drying may be in any usual manner as mayreduction by hydrogen. During the heating and reduction the organiccolloid disap ears but the nickel and fullers earth remain in theiradvantageous relation.

Instead of fullers earth, I may use other decolorizing agents; but Ifind that ordinarly fullers earth is the best for the present purposes.Other decolorizing powders, such as some of the vegetable carbons, may

.be used, but they have no advantage over 300F. may be employed,especially if the hydrogen be used in such a way as to producearelatively fine emulsion. With a very fine hydrogen emulsion, the minutebubbles tend to be taken up or adsorbed by the pores of the fullersearth and are in position to exercise a maximum activity upon' the oiland the nickel. By this operation at low.

case of high heat, is counteracted by the action of the fullers earth.After a charge of oil has been hardened and decolorized by the presentcatalyst, the catalyst may be used' with afresh charge of oil. This usemay be in methodical way, partially used catalyst being used with freshoil.

I find that as a matter of practice the activity of the nickel and thedecolorizing power of the. fullers earth last for about the same lengthof time; that is, at a time when the high activity of the nickel beginsto lessen, the decolorizing power of the :tullers earth also tends tobecome exhausted. At this time, the catalyst may be removed andextracted to regain adhering oil. It may be then extracted with nitricacid to regain the nickel and the fullers earth discarded.

Instead of nickel I may use palladium, cobalt, etc., as catalysts but Iregard nickel as particularly well adapted for the present purposes.Instead of using caustic soda I may of course use caustic potash.Carbonate of soda (sodium carbonate) and carbonate of potash (potassiumcarbonate) are good precipitants but do not dissolve wool, hide,leather, etc., with as much facility as the caustic alkali. They dohowever dissolve casein and glue quite as well.

As to the exact action of the wool or other organic colloid in theprecipitating solution, I am not aware, but the result is probably theprecipitation of nickel oxid in a highly colloid form; a form in whichit is taken up and held tenaciously in the pores of the fullers earthwhich tend toadsorb vigorously colloid mattersa fact to which a largepart of the utility of fullers earth is due. This colloid condition ofthe nickel oxid may or may not persist after the heating incident toreduction ;but it is probable that the mutual relation of the metallicnickel and surfaces of the fullers earth grains is the same after theheating as that of the nickel oxid and the surfaces before the heating.The nickel oxid being taken up by the fullers earth in a colloid form isprobably very uniformly distributed over the surfaces of the fullersearth; a fact to which the unusual activity of the preparation isprobably due. Other In this process I find that the treatment 7 improvesthe quality of the fullers earth as a decolorizing agent; this being dueto the .oil an earthy taste on treating it with fullers earth. Theseadvantages are particularly marked 1n the embodlment of my inj ventionwhere the fulle-rs earth is treated with the nickel salt andsubsequently with caustic soda in the presence of a large amount ofwater which is separated prior to drying and reducing.

These advantages are so marked that I find in practice it is desirableto give the fullers earth, prior to any other operation, a washing withcaustic soda. In so doing I take the fullers earth and boil it with astrong solution of caustic soda and then wash it thoroughly; thoroughlyenough to remove the taste of the caustic soda. It is convenient to washuntil the effluent wash water does not blue litmus. Washing may be in afilter press or any other usual way.

The so treated fullers earth may then be used to produce a catalyst inany of the Ways hereinbefore described. In so doing, the fullers earthis subjected to two treatments with caustic soda; although as a matterof fact the first treatment removes all the objectionable constituents.

In a practical embodiment of my method using a preliminary extraction,100 parts of fullers earth maybe suspended in 500 parts of a solution ofcaustic soda of 20 B.

or between 14 and 15 per cent. NaOH. The

mixture is brought to a boiling temperature and kept boiling for aboutan hour. The fullers earth may then be Washed by decantation or in afilter press until all the soluble caustic alkali is removed. Thefullers earth so prepared is then suspended in 1000 parts of water and100 parts of nickel nitrate added in solution in 300 parts of water. Themixture having been brought to a boil to permit the fullers earth totake up the nickel salt, a solution of 27.5 parts of NaOH dissolved in250 parts of water is added. This solution, like that previouslydescribed, is best first treated by dissolving two parts of wool orother colloid nitrogenous matter therein. The fullers earth is againwashedby decantation or in a filter press until no soluble salts remain.The precipitate is then pressed, dried and reduced with hydrogen. 7

Fullers earth which has been first treated with caustic soda in themanner described to free-it of all ingredients soluble in alkagenationmay be performed at much lower temperatures than those usually employedand in less time. In some cases the reduction in time required forhardening to the same degree is 50 per cent. The usual nickel catalyzersrequire temperatures between 320 and 400 F. but with a fullers"earthcarrier which has been previously treated in the manner described notonly are the other advantages of my invention obtained but hydrogenationcan be performed at 260 R; which is a very convenient temperature and atemperature at which the development of color to be removed by thefullers earth is much lessened. The nickel catalyzer so obtained isunusually long lived and since the amount of color to be removed by thefullers earth is lessened by the low temperature the compound catalystmay be employed for a longer time.

I find that the described preliminary treatment of a-carrier with astrong caustic soda solution is useful in producing compound materialsuseful in both decolorizing and hydrogenating and containing nickel in avery sensitive form. As the base of these compound atalyzers I may usein lieu of fullers earth other porous materials having a strongadsorptive power for coloring matter, such as the vegetable carbonpreparations now known on the market as decolorizing carbons.

What I claim is 1. The process of making a non-sliming decolorizingcatalyst which comprises impregnating a decolorizing powder with anickel salt, precipitating the nickel in the 4. The process of making anon-sliming decolorizating catalyst which comprises impregnatin fullersearth with a nickel salt, precipitating the nickel in the pores of thematerial with a solution carrying dissolved wool, drying and reducing.

5. The process of making a non-sliming decolorizing sensitive catalystwhich comprises treating a decolorizing powder with a boiling solutionof caustic soda, freeing from alkali, impregnating with a nickel salt,precipitating the nickel in the pores of the material with a solutioncarrying a dissolved nitrogenous organic colloid, drying and redncing. I6. he process of making a non-shmlng ('lOCOlOIJZIDg sensitive catalystWlllOll comprises treating a decolorizing powder with a boiling solutionof caustic soda, freeing from alkali, impregnating with a nickel salt,"

precipitating the nickel in the pores of the material with a solutioncarrying dissolved wool, drying and reducing.

7. The process of making a non-sliming decolorizing catalyst whichcomprises wash. ing fullersearth with a boiling solution of causticsoda, freeing from alkali, impregble matters are removed, removingthe'alsoda until all alkali-soluble matters are removed, removing thealkali by washing, im-

pregnating with a nickel compound and reduclng.

10. As a new catalyst, a porous pulverulent material having highadsorbing power for coloring matters and carrying colloidal nickel inits pores, said material being free of alkali soluble substances.

11. As a-new catalyst, fullers earth carrying colloidal nickel in itspores. Y

12. As a new catalyst, fullers earth freed of alkali-soluble matters andcarrying colloidal nickel in its pores.=

In testimony whereof, I aifix my signature.

ALEXANDER, SCHWARCMAN.

